Gels formed from amino-acid derivatives, their novel rheology as probed by bulk and particle tracking rheological methods

Abstract We discuss the use of dynamic light scattering based particle micro-rheology to probe the lengthscale dependence of the microstructures formed by Fmoc-tyrosine gels. Past studies on these systems using dye diffusion have shown that Fmoc-tyrosine is capable of forming gels that can entrap molecules if they are large enough, unlike those gels formed by Fmoc-phenylalanine (Sutton et al., 2009). This result seems at odds with microscopic studies of the gel microstructure, which indicate porosity on much larger lengthscales than the molecular probes used. Here, we use particle probe based micro-rheology to investigate the porosity of the gels on larger lengthscales than is possible using molecular diffusion studies and show that there is considerable evidence of larger scale structures present in the gel. In particular we see that at no point does particle probe based micro-rheology reproduce the bulk properties of the gels, and also that there is strong dependence of the probe behaviour on particle size. Both of these results indicate the presence of microstructural features in the gel that are of the order of the particle size.

[1]  R. Larson The Structure and Rheology of Complex Fluids , 1998 .

[2]  Thomas G. Mason,et al.  Estimating the viscoelastic moduli of complex fluids using the generalized Stokes–Einstein equation , 2000 .

[3]  E. Fedorov,et al.  Multiple-particle tracking measurements of heterogeneities in solutions of actin filaments and actin bundles. , 2000, Biophysical journal.

[4]  M. Solomon,et al.  Probe size effects on the microrheology of associating polymer solutions. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[5]  D. N. Pinder,et al.  Microrheological studies offer insights into polysaccharide gels , 2008 .

[6]  A. Donald,et al.  A microrheological study of hydrogel kinetics and micro-heterogeneity , 2014, The European physical journal. E, Soft matter.

[7]  Douglas E. Smith,et al.  Onset of Non-Continuum Effects in Microrheology of Entangled Polymer Solutions , 2014 .

[8]  Daolin Ma,et al.  Ratchet rotation of a 3D dimer on a vibrating plate , 2014, The European physical journal. E, Soft matter.

[9]  D. Weitz,et al.  Microrheology of cross-linked polyacrylamide networks. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

[10]  D. Reichman,et al.  Anomalous diffusion probes microstructure dynamics of entangled F-actin networks. , 2004, Physical review letters.

[11]  Eric M Furst,et al.  Microrheology of the liquid-solid transition during gelation. , 2008, Physical review letters.

[12]  Todd M. Squires,et al.  Fluid Mechanics of Microrheology , 2010 .

[13]  F. MacKintosh,et al.  Dynamic shear modulus of a semiflexible polymer network , 1998 .

[14]  A. Donald,et al.  Micro-scale kinetics and heterogeneity of a pH triggered hydrogel , 2012 .

[15]  A. E. Bailey,et al.  Microrheology and structure of a yield-stress polymer gel. , 2006, Physical review. E, Statistical, nonlinear, and soft matter physics.

[16]  W. Svendsen Self-assembled peptide nanostructures : advances and applications in nanobiotechnology , 2012 .

[17]  S. Edwards,et al.  The Theory of Polymer Dynamics , 1986 .

[18]  Ian W. Hamley,et al.  Self-assembly of amphiphilic peptides , 2011 .

[19]  D. Pochan,et al.  Rheological Properties of Peptide-Based Hydrogels for Biomedical and Other Applications , 2010 .

[20]  A. Donald,et al.  Microrheology and microstructure of Fmoc-derivative hydrogels. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[21]  Kelly M. Schultz,et al.  Microrheology of biomaterial hydrogelators , 2012 .

[22]  K. Schätzel,et al.  Accuracy of photon correlation measurements on nonergodic samples. , 1993, Applied optics.

[23]  P. Topham,et al.  Peptide conjugate hydrogelators , 2010 .

[24]  Neil L. Campbell,et al.  Controlled release from modified amino acid hydrogels governed by molecular size or network dynamics. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[25]  D A Weitz,et al.  Microrheology of polyethylene oxide using diffusing wave spectroscopy and single scattering. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[26]  Denis Wirtz,et al.  Rheology and microrheology of semiflexible polymer solutions : Actin filament networks , 1998 .

[27]  William J Frith,et al.  The influence of the kinetics of self-assembly on the properties of dipeptide hydrogels. , 2013, Faraday discussions.

[28]  A. Donald,et al.  Particle tracking microrheology of gel-forming amyloid fibril networks , 2009, The European physical journal. E, Soft matter.

[29]  D A Weitz,et al.  Investigating the microenvironments of inhomogeneous soft materials with multiple particle tracking. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[30]  David A. Weitz,et al.  Nanomechanics of vimentin intermediate filament networks , 2010 .

[31]  J. Lu,et al.  Molecular self-assembly and applications of designer peptide amphiphiles. , 2010, Chemical Society reviews.

[32]  Paul Sanderson,et al.  A new method for maintaining homogeneity during liquid–hydrogel transitions using low molecular weight hydrogelators , 2009 .

[33]  E. Botvinick,et al.  Characterization of hydrogel microstructure using laser tweezers particle tracking and confocal reflection imaging , 2010, Journal of physics. Condensed matter : an Institute of Physics journal.